The deterioration of paper, books and newspapers is well-known and of growing concern to librarians and archivists throughout the world. The causes of paper deterioration are numerous and include inherent acidity, photodegradation, oxidation, and even microbiological attack under certain conditions. These factors combined with initial paper quality have severely reduced the permanence of library and archival collections. It is becoming generally accepted that the most insidious problem is the acidity of most book paper produced in the last one hundred years.
The demand for large amounts of printing paper over the last century led to the introduction of pulp fiber produced from wood by chemical or mechanical means. However, paper made from untreated wood pulp is too absorbent to allow sharp image imprint. Therefore, chemicals have to be added to the wood fibers during processing. These additives allow the paper to accept inks and dyes and increase paper opacity. Unfortunately, most of these chemicals are either acidic or are deposited by acidic mechanisms which initiate the slow, but relentless acidic deterioration of paper. Other contributions to the acidification of paper are supplied by man through industrial emissions of sulfur and nitrogen and carbon oxides or by natural processes such as sea salt spray. Even books or paper of neutral and alkaline characters are not immune. As neighboring papers of acidic nature degrade, volatile acids are produced which either diffuse through adjoining books or permeate the atmosphere and may ultimately acidify even the "safe or stable" books.
In order to arrest this acidic degradation, paper materials must be deacidified and provided with an alkaline reserve or buffer to retard a return to an acidic state. There are several known processes for deacidifying paper whether bound or unbound. Numbering among these are processes using volatile metal alkyls, e.g. U.S. Pat. Nos. 3,969,549, and 4,051,276, and volatile amines e.g. U.S. Pat. Nos. 3,472,611, 3,771,958 and 3,703,353. U.S. Pat. No. 3,676,182 describes the treatment of cellulosic materials with alkali and alkaline earth bicarbonates, carbonates, and hydroxides in a halogenated hydrocarbon solvent or lower aliphatic hydrocarbon such as n-butane with an optional plasticizing agent such as ethylene glycol. U.S. Pat. No. 3,676,055 to Smith describes a nonaqueous deacidification solution for treating cellulosic materials comprising 1000 cc of 7 percent magnesium methoxide in methanol and in addition 20 pounds of dichlorodifluoromethane (Freon 22). Canadian Patent No. 911,110 to Smith describes a deacidification solution of a 7% magnesium methoxide solution in methanol (10 parts) and a halogenated solvent or solvents (90 parts): and states that a magnesium alkoxide reacts with water in paper to form a mildly alkaline milk of magnesia, being magnesium hydroxide. Improved results are reported with the use of the halogenated hydrocarbon solvents.
Unfortunately, all of these processes suffer from one or more of a number of drawbacks that have prevented their wide-spread acceptance. These drawbacks include high cost, toxicity, complexity of treatment, residual odor, deleterious effects on certain types of paper and inks, lack of an alkaline reserve, and the necessity of drying the book or paper to very low moisture contents before treatment.
Kundrot, U.S. Pat. No. 4,522,843, provided a solution to the problems experienced with prior art systems. The method of the Kundrot patent utilizes a dispersion of alkaline particles of a basic metal oxide, hydroxide or salt, such as magnesium oxide, in a gas or liquid dispersant. The MgO, when converted to Mg(OH).sub.2, according to the reaction MgO+H.sub.2 O.fwdarw.Mg(OH).sub.2 effectively neutralizes the initial acidity in the paper and provides an adequate alkaline reserve to counter future re-acidification. The deacidification reactions occur later (a period of days) and are typically described as Mg(OH).sub.2 +H.sub.2 O.sub.4 .fwdarw.MgSO.sub.4 +2H.sub.2 O. The liquid dispersant or carrier, described in the Kundrot patent is an inert halogenated hydrocarbon. It does not take part in the deacidification, but serves to carry the particles to the fabric of the paper. In several embodiments described, the halogenated hydrocarbons are Freons, or chlorofluorocarbons (CFC). CFC's have since been found to harm public health and the environment by depleting ozone in the upper atmosphere. Manufacturers of CFC's presently place limits on the amounts they will sell to any one purchaser and are phasing out production of CFC's entirely.
A replacement for the CFC carrier in the method of deacidifying books and other cellulose based materials described in the Kundrot patent was described in Leiner et al., U.S. Pat. No. 5,409,736. The Leiner patent replaced the CFC's of the Kundrot patent with perfluorinated carriers, such as perfluoropolyoxy ether and perfluoromorpholine. Unlike CFC's, perfluorocarbons are not known to cause damage to the ozone layer. However, perfluorocarbons are classified as greenhouse gases because they decompose slowly and trap heat in the atmosphere.